JP2022146935A - Silane functionalized styrenic block copolymer - Google Patents

Abstract

To provide a silane functionalized block copolymer (SiHSBC) comprising 80 to 99.90 wt.% of a hydrogenated styrenic block copolymer (HSBC) and 0.1 to 20 wt.% of a silane, based on the total weight of the SiHSBC.SOLUTION: The HSBC is obtained by hydrogenation of a styrenic block copolymer (SBC) comprising at least one polymer block A derived from a vinyl aromatic monomer, and at least one polymer block B derived from a conjugated diene monomer. The polymer block B has more than 80 wt.% of a polymerized 1,3-butadiene monomer, based on the total weight of the polymerized conjugated diene monomer in the polymer block B. The SiHSBC and a thermoplastic elastomer composition containing the SiHSBC show improved adhesion to polar and non-polar substrates without the need of an adhesive layer or primer layer.SELECTED DRAWING: None

Description

The present disclosure relates to silane-functionalized styrenic block copolymers, compositions and methods for their preparation.

Substrate materials based on glass, ceramics, and metals have high heat resistance, better mechanical properties, and high durability, and are widely used in appliances, electronic components, auto parts, solar panels, and many other applications. useful in In some applications, these materials adhere to or form composites with thermoplastic elastomers. The flexibility and ease of processing of thermoplastic elastomers make such materials suitable for the manufacture of structural members, shock absorption, damage protection, and sealing. However, thermoplastic elastomers, such as styrenic thermoplastic elastomers, are poorly polar and the adhesive strength between such elastomers and polar substrates is not sufficient for some end-use applications.

The use of adhesion promoters/primers has been attempted to improve the adhesive strength of thermoplastic elastomers to substrates such as polar and non-polar substrates. Another commonly known approach to obtaining better adhesion is surface treatment of the substrate prior to application of the thermoplastic elastomer. Silane-functionalized block copolymers provide better adhesion to substrates, but other properties such as flexibility, elasticity, processability, storage stability, process stability, clarity, mechanical properties, etc. may have an impact.

Accordingly, there is a need for improved silane-functionalized block copolymers that increase adhesion to substrates without affecting other properties.

(Summary)
In a first aspect, the present disclosure provides (a) 80 to 99.90 wt% hydrogenated styrene block copolymer (HSBC), and (b) 0.1 to 0.1 wt%, based on the total weight of the silane-functionalized block copolymer. It relates to a silane-functionalized block copolymer (SiHSBC) comprising, consisting essentially of, or consisting of 20% by weight of silane. The silane has the general formula (I) of RR' _n SiX _3-n , where R is an alkene or alkyne group, R' is H or an alkane group, X is an alkoxy group, n=0, is 1 or 2]. HSBC is obtained by hydrogenating a styrenic block copolymer (SBC) comprising at least one polymer block A derived from a vinyl aromatic monomer and at least one polymer block B derived from a conjugated diene monomer. Polymer block B has a hydrogenation level of greater than 95 mol% relative to the total moles of polymerized conjugated diene monomers in polymer block B and greater than 80% by weight relative to the total weight of polymerized conjugated diene monomers in polymer block B. of polymerized 1,3-butadiene monomer. HSBC has a rubbery aliphatic methyl index (RAMI) of 18-38 and a polystyrene content (PSC) of 10-45% by weight based on the total weight of the hydrogenated styrene block copolymer. SiHSBC has a peel adhesion strength to glass substrates greater than 20 N/cm, measured according to ASTM F88.

In a second embodiment, the HSBC has a viscosity of ≤1800 mPa.s at 25 wt% in toluene at 25°C. It has a solution viscosity of s.

In a third embodiment, polymer block A has a molecular weight (M _p ) of 3-45 kg/mol and polymer block B has a molecular weight (M _p ) of 5-400 kg/mol.

In a fourth aspect, the HSBC has a molecular weight (M _p ) of 40-500 kg/mol.

As used herein, the following terms have the following meanings.

"At least one of [groups such as A, B and C]" or "any of [groups such as A, B and C]" refers to a single member from a group, multiple members from a group or a combination of members from a group. For example, at least one of A, B and C is, for example, only A, only B or only C, and A and B, A and C, B and C, or A, B and C, or A, B and all other combinations of C. A list of embodiments indicated as "A, B or C" includes embodiments A only, B only, C only, "A or B", "A or C", "B or C" or "A, B or C".

"Copolymer" refers to a polymer derived from more than one species of monomer.

"Block copolymer" refers to a copolymer comprising more than one type of monomer, wherein the polymerized monomers are in blocks. Each block is composed of a series of monomers that is different from the series of monomers of the surrounding blocks to which it is attached in the same block copolymer. Each block may be composed of homopolymers or random copolymers.

A "plasticizer" is used to make a material softer, more flexible, or to increase the plasticity of a material, or to reduce the viscosity of a material, or to reduce friction during handling of the material in the manufacturing process. A chemical compound added to a material to Plasticizers are added to polymers such as plastics and rubbers to facilitate handling of raw materials during manufacturing or to meet end-use application requirements.

"Order-disorder transition temperature" or ODT refers to the temperature at which a block copolymer transitions between phase separated and non-phase separated states. ODT is defined as the temperature above which zero shear viscosity can be measured by dynamic rheology. The ODT temperature can be measured using dynamic mechanical analysis (DMA), where a temperature sweep is performed with varying frequencies, and the ODT is identified as the temperature at which the complex viscosities begin to merge into a single value at low frequencies. be done.

"Coupling efficiency" or CE refers to the weight percent of coupled and uncoupled polymer. The weight percent of coupled and uncoupled polymer can be determined using GPC and differential refractometer (RI) detector output. The intensity of the signal at a particular elution volume is proportional to the amount of material detected in that elution volume. The area under the curve over the _MW range corresponding to coupled polymer represents the weight percent of coupled polymer, as well as the weight percent of uncoupled polymer. The percentage of CE is obtained by multiplying the weight percent of coupled polymer/(weight percent of coupled polymer+weight percent of uncoupled polymer) by 100. CE also calculated the data from GPC and calculated the integrated area under the GPC curve for all coupled polymers (including 2-arm, 3-arm, 4-arm, etc. copolymers) It can be evaluated by dividing by the integrated area under the same GPC curve for both of the untreated polymers.

The "polystyrene content" or PSC of a block copolymer refers to the weight percent of polymerized vinyl aromatic monomer, e.g., styrene, in the block copolymer, divided by the sum of the molecular weights of all polymerized vinyl aromatic units divided by the total molecular weight of the block copolymer. calculated by PSC can be determined using any suitable method, such as proton nuclear magnetic resonance (NMR).

The "rubber aliphatic methyl index" or RAMI in a polymer is related to the specific vinyl content of the polymerized 1,3-butadiene monomer in the polymer prior to hydrogenation. For example, a RAMI of 18-38 is the total moles of polymerized 1,3-butadiene monomer in the polymer (provided that all of the polymerized 1,3-butadiene monomer is hydrogenated) per 1,3-butadiene monomer before hydrogenation. This corresponds to a vinyl content of 48-100 mol % of the polymerized 1,3-butadiene monomer. RAMI is adjusted to remove the contribution of aliphatic protons from the protons of polymerized vinyl aromatic monomers (e.g., polymerized styrene units), followed by rubbery units (e.g., polymerized 1,3-butadiene monomer, It can be calculated as the ratio of the aliphatic protons (H) present in the methyl groups of the hydrogenated polymerized conjugated diene monomer to the total aliphatic protons present in the polymerized conjugated diene monomer (such as polymerized isoprene monomer). can. Aliphatic protons (H) can be measured using H-1 NMR spectroscopy. RAMI is expressed as:
RAMI=100*(integral 2)/(integral 1-(0.6*integral 3))
where integral 1 is obtained by integrating the H-1 NMR spectrum from 0.6 ppm to 2.99 ppm, integral 2 is the H −1 Determined by integrating the NMR spectrum. Integral 3 is obtained by integrating the H-1 NMR HSBC spectrum from 6.2 ppm to 7.4 ppm.

"Molecular weight" or Mw refers to the polystyrene equivalent molecular weight in kg/mol of a polymer block or block copolymer. Mw can be measured using gel permeation chromatography (GPC) using polystyrene calibration standards, eg, according to ASTM 5296-19. GPC detectors may be ultraviolet or refractive index detectors or a combination thereof. The chromatograph is calibrated using commercially available polystyrene molecular weight standards. The Mw of a polymer measured using GPC calibrated in this way is the polystyrene equivalent molecular weight or apparent molecular weight. The Mw given herein is measured at the peak of the GPC trace and is commonly referred to as the polystyrene equivalent "peak molecular weight", denoted _Mp . If the polymer GPC exhibits several peaks, the _Mp chosen is the peak molecular weight of the major species (largest in weight percent).

"Transparency" refers to light transmission through an object. Clarity can be measured according to ASTM D-1003. This test method evaluates the total light transmission and scattering of transparent objects of defined specimen thickness.

"Clarity" refers to the property of a material that can produce an opaque or dulling effect when light is scattered through a flat material. Objects therefore appear hazy when viewed through the material.

"Thermoplastic block copolymer" refers to a block copolymer that can be processed at higher temperatures and is not intentionally crosslinked prior to processing.

The present disclosure functionalizes or grafts 80 to 99.90 wt% hydrogenated styrene block copolymer (HSBC) with 0.1 to 20 wt% silane compound based on the total weight of silane functionalized block copolymer (SiHSBC). It relates to SiHSBC obtained by reducing SiHSBC improves adhesion to polar and non-polar substrates such as glass, silicon wafers, ceramics, metals, plastics, reinforcing fibers, etc. without the need for a layer of adhesive or primer.

Hydrogenated Styrene Block Copolymer (“HSBC”): HSBC is a thermoplastic block copolymer obtained by hydrogenation of a styrenic block copolymer (SBC).

In embodiments, the SBC is either a linear or branched (multi-arm) block copolymer comprising at least one polymer block A derived from a vinyl aromatic monomer and at least one polymer block B derived from a conjugated diene monomer. or The vinyl aromatic monomers can be introduced or copolymerized into the conjugated diene blocks in any order and in any distribution.

In embodiments, SBC is AB, ABA, (AB) _n X, ABB', (ABB') _n X, AIB- having a structure selected from the group of IA, (AIB) _n -X and mixtures thereof, wherein n is a positive integer and X is the residue of a coupling agent , each I is a polymer block of predominantly polymerized isoprene monomers. In embodiments, polymer blocks B and B' are the same or different and are selected from the group of polybutadiene, poly(isoprene-r-butadiene) and poly(butadiene-r-styrene), wherein -r- refers to a random copolymer, for example, "poly(isoprene-r-butadiene)" means a polyisoprene butadiene random copolymer.

In embodiments, the vinyl aromatic monomer is styrene, α-methylstyrene, methylstyrene, p-methylstyrene, ethylstyrene, propylstyrene, butylstyrene, tert-butylstyrene, dimethylstyrene, vinyltoluene, vinyltoluene isomers. vinylxylene, 1,1-vinylbiphenyl, vinylnaphthalene, vinylanthracene and mixtures thereof.

In embodiments, the conjugated diene monomer is 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1-phenyl-1,3-butadiene, 1,3-pentadiene, 1,3- It is selected from the group of hexadiene, 3-butyl-1,3-octadiene, myrcene, farnesene, 1,3-cyclohexadiene, piperylene and mixtures thereof.

In embodiments, polymer block B comprises polymerized 1,3 - with butadiene monomer.

In embodiments, the polymerized 1,3-butadiene monomer in polymer block B is from 48 to 95 or from 50 to 90 or from 55 to 85, based on the total weight of polymerized 1,3-butadiene monomer, before hydrogenation. , 60-85 or >55% or <90% by weight.

In embodiments, polymer block A, which is derived from polymerized vinyl aromatic monomers, remains essentially unhydrogenated, and polymer block B, which is based on polymerized conjugated diene monomers, is hydrogenated. In embodiments, polymer block A has a hydrogenation level of <30 or <20 or <10 or <5 mol % relative to the total moles of vinyl aromatic monomer polymerized. In embodiments, polymer block B has a hydrogenation level of >70 or >80 or >90 or >95 or >98 or >99 mol% relative to the total moles of polymerized conjugated diene monomer in polymer block B . Hydrogenation level refers to the percentage of original unsaturated bonds that become saturated upon hydrogenation, which can be determined using UV-VIS spectrophotometry and/or proton NMR and/or ozonolytic titration.

In embodiments, the SBC is styrene-butadiene (SB), styrene-butadiene-styrene (SBS), styrene-isoprene (SI), styrene-isoprene-styrene (SIS), styrene-isoprene/butadiene (SI/ B), styrene-isoprene/butadiene-styrene (SIBS), styrene-butadiene/styrene (S-B/S), styrene-butadiene/styrene-styrene (S-B/S-S), styrene-isoprene/styrene ( SI/S), styrene-isoprene/styrene-styrene (SI/SS) and mixtures thereof, but not limited thereto. In embodiments, the HSBC is styrene-ethylene/butylene-styrene (SEBS), styrene-ethylene/butylene (SEB), styrene-ethylene/propylene-styrene (SEPS), styrene-ethylene/ethylene/propylene-styrene (SEEPS ), styrene-ethylene/butylene/styrene-styrene (SE/B/SS) and mixtures thereof, but not limited thereto.

In embodiments, polymer block A has a molecular weight (M _p ) of 3-45 or 3.5-30 or 4-25 or 4.5-20 or 5-15, 5-10 kg/mol.

In embodiments, polymer block B has a molecular weight (M _p ) of 5-400 or 10-250 or 15-150 or 5-80 or 20-70 kg/mol.

In embodiments, the HSBC has a molecular weight (M _p ) of 40-500 or 50-300 or 60-200 or 70-150 or 80-120 kg/mol.

In embodiments, the HSBC has a polystyrene content (PSC) of 8-45 or 10-40 or 12-35 or 14-30, 15-25 weight percent based on the total weight of the HSBC.

In embodiments, the HSBC has an order-disorder transition temperature (ODT) of <300°C or 150-300°C or 170-280°C or 180-260°C, 190-250°C.

In embodiments, the HSBC has a Rubbery Aliphatic Methyl Index (RAMI) of 18-38 or 19-36 or 20-35 or 22-34 or 25-32.

In embodiments, the HSBC is ≤1800 mPa.s at 25 wt% in toluene at 25°C. s or <1600 mPa.s s or <1400 mPa.s s or 50-1800 mPa.s. s or 80-1200 mPa.s. It has a solution viscosity of s.

Silanes for functionalization/grafting: HSBC have the general formula (I): RR' _n SiX _{3-n where} R is an alkene or alkyne group, R' is H or an alkane group, X is an alkoxy group and n=0, 1 or 2], yields silane-functionalized block copolymers (SiHSBC). In embodiments, R groups are selected from the group vinyl, allyl, butenyl, cyclohexenyl, cyclopentadienyl, and the like. R' can be selected from H or C ₁ -C ₁₀ alkanes and X can be selected from the group of methoxy, ethoxy, butoxy, acyloxy and the like.

Examples of suitable silanes include vinyltrimethoxysilane (VTMOS), vinyltriethoxysilane (VTEOS), vinyltributoxysilane, vinyldimethoxyethoxysilane, vinyldimethoxybutoxysilane, vinyldiethoxybutoxysilane, allyltrimethoxysilane, allyl triethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, dimethoxymethylsilane, diethoxymethylvinylsilane, p-styryltrimethoxysilane, p-styryltriethoxysilane and mixtures thereof; , but not limited to them.

The amount of silane added to the HSBC varies based on the desired level of silane functionalization. Generally, this amount is in the range of 0.1-20 or 0.5-15 or 1-12 or 2-10% by weight based on the combined weight of HSBC and silane.

A sufficient level of silane grafting to the HSBC is necessary to obtain the desired adhesion of the SiHSBC to substrates such as glass, silicon wafers, ceramics, metals, plastics, reinforcing fibers, and the like. In embodiments, the level of silane grafted onto the HSBC (degree of silane functionalization) is 0.1 to 20 or 0.2 to 15 or 0.5 to 12 or 0.1 based on the total weight of SiHSBC. ~10 or 0.2 to 5 or 0.2 to 4.

When silane is added to HSBC for grafting, some may be left ungrafted. In embodiments, the amount of ungrafted silane is <40 or <30 or <20 or <10 wt% based on the total weight of silane added to graft the HSBC.

In embodiments, after grafting silane onto HSBC to form SiHSBC, the SiHSBC has a molecular weight (M _p ) of 45-250 or 50-220 or 60-200 kg/mol.

Method of making SiHSBC: First, an SBC containing at least one polymer block A and at least one polymer block B is prepared. SBCs can be prepared by anionic polymerization or by sequential (or continuous) polymerization. In embodiments, polymerization of the monomers is accomplished by stepwise addition of the monomers to a solution containing the initiator, followed by coupling of the resulting sequential block copolymer chains with a coupling agent (if present). be implemented.

In embodiments, the SBC is prepared by sequential polymerization at temperatures of -30 to 150°C or 10 to 100°C or 30 to 90°C using steps similar to those used for anionic polymerization. It is carried out in an inert atmosphere, eg nitrogen, or under a pressure in the range of about 0.5 to 65 bar. Polymerization generally requires <12 hours or 5 minutes to 5 hours, depending on factors including temperature, concentration of monomer components, molecular weight of the polymer, and the like.

In embodiments involving coupling, the coupling agent is a di- or multi-vinyl arene compound; a di- or multi-epoxide; a di- or multi-isocyanate; a di- or multi-alkoxysilane; aldehydes; di- or multiketones; alkoxytin compounds; di- or multihalides such as silicon halides and halosilanes; mono-, di- or multianhydrides; diesters that are esters of monohydric alcohols with dicarboxylic acids; diesters that are esters of monobasic acids with polyhydric alcohols such as glycerol; and mixtures thereof, but only to Not exclusively.

In embodiments, silane-based coupling agents are used in the preparation of coupled SBCs. In embodiments, the silane as coupling agent and the silane compound as functionalizing agent are the same or different.

In embodiments, any effective amount of coupling agent is used to obtain the desired coupling efficiency for SBC. In embodiments, the SBC has a coupling efficiency of >50% or >60% or >70% or >80% or >90% when coupled.

A hydrogenation process is then used to hydrogenate the SBC precursor to yield a hydrogenated styrene block copolymer (HSBC). HSBC can be prepared using a hydrogenation process that is selective for the double bonds of the conjugated diene block and leaves the aromatic unsaturation of the polystyrene block substantially intact.

In embodiments, the hydrogenation process uses a catalyst or catalyst precursor comprising a metal, eg nickel, titanium or cobalt, and a suitable reducing agent such as an alkylaluminum. The catalyst concentration is in the range of 10-500 ppm by weight. Hydrogenation of SBC is controlled by using relatively low hydrogenation temperatures in the range of 25-175°C or 35-150°C or 50-100°C. Hydrogenation is generally carried out within the range of 5 minutes to 8 hours or 30 minutes to 4 hours. Hydrogenation can be carried out in an autoclave at hydrogen pressures of less than about 3000 psig or 100-1500 psig or 200-800 psig. After hydrogenation is complete, the catalyst and catalyst residues are separated from the polymer.

Functionalization/Grafting of HSBC with Silane: In embodiments, grafting of silane onto HSBC is performed at a temperature of 160-240° C. or 170-230° C. or 180-220° C. using equipment known in the art; It is carried out in the melt phase, for example by means of a single-screw extruder or a twin-screw extruder.

In embodiments, the SiHSBC is prepared by solid state methods. HSBC, silane and initiator are used for solid phase silane functionalization in a reactor at temperatures ranging from 40° C. to the melting or softening temperature of HSBC. SiHSBC with a degree of silane functionalization of 0.1-20 wt% is discharged at the end of the reactor.

Examples of initiators include organic peroxides, which are capable of generating free radicals in HSBC at given reaction temperatures resulting in half-lives of <6 minutes or <1 minute at the functionalization temperature. . In embodiments, organic peroxides include dicumyl peroxide (DCP) and 1,3-bis(tert-butylperoxyisopropyl)benzene, diacyl peroxide, alkyl peresters, percarbonates, dilauroyl peroxide (DLPO) , dibenzoyl peroxide (DBPO), tert-butylperoxy-2-ethylhexanoate (TBPEH), tert-butylperoxy-isobutyrate (TBPIB), 1,1-di-(tert-butylperoxy)cyclohexane (DTBPC), tert-butyl perbenzoate (TBPB), 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (DHBP), 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne- 3 (DYBP), di-tert-butyl peroxide (TBP), cumene hydroperoxide (CHP), tert-butyl hydroperoxide (TBHP), lauroyl peroxide, dipropionyl peroxide, p-menthane hydroperoxide and mixtures thereof Selected from, but not limited to, the group.

In embodiments, an organic peroxide that forms free radicals with a one minute half-life temperature in the range of 50-160°C or 60-150°C or 70-140°C grafts the silane onto the HSBC in a melt phase extrusion process. or in a solid phase functionalization method at a reaction temperature of 50-200°C.

In embodiments, the initiator is added in an amount of 0.01-5 or 0.1-2 or 0.2-1 wt% based on the combined weight of HSBC and silane.

In embodiments, SiHSBC is crosslinked by treatment with water or moist air. The water can be hot water/steam at a temperature of 40-90° C. or 65-85° C. or 70-80° C. for 0.5-12 hours or 1-10 hours or up to 1 week or more.

Compositions Based on Silane-Functionalized Block Copolymers: In embodiments, the thermoplastic polymer composition comprises 5 to 95 parts by weight SiHSBC and 5 to 95 parts by weight, based on the total weight of the thermoplastic polymer composition. part thermoplastic elastomer compound (TPEC).

A thermoplastic elastomer compound (TPEC) comprises one or more thermoplastic elastomers (TPE) and 50 to 250 parts of plasticizer and 0 to 50 parts of at least one additive per 100 parts by weight of TPE. Refers to composition. In embodiments, the TPE is a polyolefin, a hydrogenated styrenic block copolymer-based TPE (TPE-HSBC), a styrenic block copolymer-based TPE (TPE-SBC), a thermoplastic copolyester or a copolyester-ether (TPE-E), thermoplastic vulcanizates (TPE-V), thermoplastic polyurethanes (TPE-U) and mixtures thereof.

Alternatively, the thermoplastic polymer composition can be formulated without TPEC, simply with either plasticizers or polyolefins. In embodiments, a SiHSBC and a thermoplastic polymer composition comprising 0-150 parts polyolefin, 30-300 parts plasticizer, and 0-50 parts at least one additive per 100 parts by weight SiHSBC . In embodiments, the thermoplastic polymer composition comprises SiHSBC and 10-150 parts polyolefin, 0-300 parts plasticizer, and 0-50 parts at least one additive per 100 parts SiHSBC by weight. A thermoplastic polymer composition.

Polyolefins include polypropylene, polyethylene, high density polyethylene (HDPE), low density polyolefin (LDPE), linear low density polyethylene (LLDPE), ultra high molecular weight polyethylene (UHMW-PE), linear low density polyethylene (LLDPE), ultra Low density polyethylene (VLDPE), ethylene and 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, etc. It can be selected from, but not limited to, the group of copolymers of α-olefins with C ₃ -C ₂₀ comonomers, ethylene-propylene copolymers such as random polypropylene or block polypropylene, and mixtures thereof.

In embodiments, the thermoplastic polymer composition includes other polymers such as acrylonitrile-butadiene-styrene, polylactic acid, polyamides, polyphenylsulfones, polycarbonates, polyethylene/acrylonitrile-butadiene-styrene, polycarbonates/acrylonitrile -butadiene-styrene, methyl methacrylate/acrylonitrile-butadiene-styrene, polyetherimides, ethylene-vinyl alcohol copolymers, polyesters, poly(vinylidene chloride), polyphenylene ethers, cellulose, polyacrylates, polymethacrylates, polystyrenes and mixtures thereof. include.

Typical additives include activators, hardeners, stabilizers, neutralizers, thickeners, coalescing aids, slip agents, release agents, antimicrobial agents, surfactants, antioxidants, and antiozonants. agents, color change pH indicators, plasticizers, tackifiers, film-forming additives, dyes, pigments, crosslinkers, UV absorbers, UV stabilizers, catalysts, fillers, other resins, redox couples, fibers, flame Repellents, viscosity modifiers, wetting agents, degassing agents, reinforcing agents, adhesion promoters, colorants, heat stabilizers, light stabilizers, lubricants, fluidity modifiers, anti-drip agents, anti-blocking agents, anti-static agents , processing aids, stress relieving additives, waxes and mixtures thereof.

Plasticizers can be selected from the group of vegetable oils, process oils, mineral oils, phthalates and mixtures thereof. Processing oils may include one or more components of the group consisting of paraffinic oils, naphthenic oils. In embodiments, paraffinic oils are saturated carbon skeletons and naphthenic oils have polyunsaturated carbon or cyclic structures containing substantially no aromatics.

Waxes may be natural waxes, petroleum-derived waxes and mixtures thereof.

Representative non-reactive fillers include _CaCO3 , carbon black, graphite and mixtures thereof. Typical reactive fillers include silica, glass beads, sand, talc, mica, clay, wollastonite, Mg(OH) ₂ , Al(OH) ₃ , iron oxide, tin oxide and mixtures thereof. A reactive filler as meant herein is a filler material that reacts with a silane compound.

In embodiments, the thermoplastic polymer composition is prepared by equipment known in the art, such as blenders, mixers, kneaders, rollers, twin screw extruders or extruders.

In embodiments, the thermoplastic polymer composition is prepared by dry blending the components of the composition. Alternatively, thermoplastic polymer compositions can be prepared by mixing the ingredients in a suitable solvent. Solvents can include organic solvents such as cyclohexane, naphtha, toluene, ester solvents such as ethyl acetate and propyl acetate, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. The amount of solvent can be from 100 to 2000 parts for 100 parts SiHSBC.

Properties of silane-functionalized block copolymers: SiHSBC produces desirable adhesion to substrates when treated (eg, heated, in solvents, etc.). In embodiments, the substrate is glass, silicon wafer, ceramic, metal, plastic, reinforcing fiber, wood, leather, stone, concrete, rock, paper, corrugated paper, fabric, glass, brick, gypsum, cement, tile. , mortar and asphalt, but not limited to them.

In embodiments, the SiHSBC adheres to glass substrates without the need for a layer of primer after being exposed to high temperature/humidity conditions for extended periods of time, such as 1 week, 1 month, 3 months or more. Even maintains excellent adhesion to glass substrates.

In embodiments, the SiHSBC is >3 by testing at 23° C. using a Type 2 dumbbell cut from a 2 mm thick compression molded plate, measured according to ISO 37, using a pull rate of 500 mm/min. or have a tensile strength of >5 or >10 or <30 MPa.

In embodiments, the SiHSBC after cross-linking by exposure to hot water has a tensile strength of >3 or >5 or >10 or <30 MPa.

In embodiments, the SiHSBC is >20 or >30 or >40 or >50 or >60 or <100 N/cm measured according to ASTM F88 before and after aging the specimen in water at 23° C. for 1 week. It has peel adhesive strength to glass substrates.

In embodiments, the SiHSBC has a Shore A hardness of 10-70 or 20-70 or 30-60 or >15 or >20 measured according to ASTM D2240.

In embodiments, the SiHSBC has a melt flow rate (MFR) of >1 or >3 or >5 or >15 dg/min at 190° C. with a load of 2.16 kg measured according to ASTM D1238.

In embodiments, the SiHSBC has a clarity of >70% or >75% or >80% or >85% measured on a 1 mm plate.

In embodiments, the SiHSBC has a transparency of >70% or >75% or >80% or >85% for a 1 mm plate measured according to ASTM D-1003.

In embodiments, the SiHSBC has a refractive index (RI) of 1.45-1.55 or 1.48-1.54 or 1.51-1.525.

Properties of Thermoplastic Polymer Compositions: Thermoplastic polymer compositions containing SiHSBC are characterized by improved adhesion to a variety of substrates. In embodiments, the thermoplastic polymer composition is >10 or >20 or >30 or >40, >50 or <50 or <20 or >20 or >30 or >40 as measured according to ASTM F88 before and after aging the specimen in water at 23°C for 1 week. It has a peel adhesive strength to a glass substrate of 100 N/cm.

In embodiments, the thermoplastic polymer composition has a Shore A hardness of 10 to 80 or 15 to 70, <70 or <50 or >15 or >20, measured according to ASTM D2240.

In embodiments, the thermoplastic polymer composition has a melt flow rate (MFR ).

In embodiments, the thermoplastic polymer composition after curing provides a cured composition having a compression set of <80% or <70% or >40% or >50% after 24 hours at 120°C or 180°C. do.

End Use Applications: SiHSBC and its thermoplastic polymer compositions can be used to form seals for use with articles such as windows, windshields, and the like. Other industrial uses of SiHSBC and its compositions are in wires and cables, as transparent rubbery layers for solar panels, for fiber coatings, adhesives, sealants in flame retardant systems, high temperature resistant cured TPEs, etc. , primers, tie layers, encapsulants for windows.

The following examples are provided to further illustrate the disclosure, along with the properties or methods of measurement indicated below.

Materials: The following materials are used.

BC1 is a selectively hydrogenated coupling block copolymer derived from styrene and 1,3-butadiene monomers with the structure (SE/B) _n X, with a coupling efficiency of 93% and an M _p of 75 kg/mol, polystyrene content (PSC) of 20%, RAMI of 29, hydrogenation level of 99.2 mol%, MFR of 38 dg/min at 190°C and 2.16 kg load, ODT of 200°C, hardness Shore A 52, solution viscosity of 90 mPa.s measured at 25% by weight in toluene at 25°C. is s.

BC2 is a selectively hydrogenated block copolymer derived from styrene and 1,3-butadiene monomers with the structure SE/BS, M _p of 235 kg/mol, PSC of 31 wt%, RAMI 26, a hydrogenation level of 99.2 mol %, a hardness Shore A of 60 and a solution viscosity of >50 mPa.s measured at 25 wt % in toluene at 25°C. is s.

BC3 is a selectively hydrogenated block copolymer with the structure (SE/B) _n X with a coupling efficiency of 92%, an M _p of 242 kg/mol, a PSC of 13 wt% and a RAMI of 30,190. MFR of 0.4 dg/min at °C and 2.16 kg load, hydrogenation level of 99 mol%, ODT of 255 °C, hardness Shore A of 35, solution viscosity of 650 mPa measured at 25 wt% in toluene at 25 °C . is s.

BC4 is a selectively hydrogenated block copolymer derived from styrene and 1,3-butadiene monomers with the structure SE/BS, M _p of 80 kg/mol, PSC of 30 wt%, RAMI is 15, MFR is 2 dg/min at 230°C and 2.16 kg load, hydrogenation level is 99.2 mol%, hardness Shore A is 70, solution viscosity measured at 25 wt% in toluene at 25°C is 1800 mPa.s. is s.

BC5 is a selectively hydrogenated block copolymer derived from styrene and 1,3-butadiene monomers. It has a SE/B/SS structure, M _p of 150 kg/mol, PSC of 60 wt %, RAMI of 14, hydrogenation level of 99.5 mol %, hardness Shore A of 79. .

BC6 is a 2 wt% maleic anhydride functionalized variant of BC4.

BC7 is a selectively hydrogenated block copolymer derived from styrene and 1,3-butadiene monomers with the structure SE/BS, M _p of 280 kg/mol, PSC of 31 wt%, RAMI 15, a hydrogenation level of 99 mol %, a hardness Shore A of 70 and a solution viscosity of 50 mPa.s measured at 25 wt % in toluene at 25°C. is greater than s.

Kristalex™ 5140 is a hydrocarbon resin with a softening point of 140°C from Eastman.

A silicate-type glass plate was used as the substrate, which was not subjected to any specific surface treatment, and had dimensions of length (L)*width (W)*height (H) = 135*25.4*. It has a dimension of 3 mm.

Preparation process of SiHSBC: SiHSBC is manufactured by extruding each of BC1-BC7 with various silanes (VTMOS and VTEOS) and peroxides using a 30 mm co-rotating twin-screw extruder. In embodiments, ingredients are added in parts per hundred parts of HSBC. The temperature profile of the extruder during functionalization, the amount of each of the silanes and the amount of peroxide are summarized in Table 1.

Table 2 shows the properties of HSBC and SiHSBC.

The effect of storage duration on MFR (190°C/2.16 kg) was evaluated for various SiHSBCs. Samples were dried and stored in aluminum foil bags at 85°C for various periods of time. Table 3 shows the MFR results.

Flowability was studied by measuring the MFR of SiHSBC (230° C./2.16 kg) versus storage time in the molten state, as shown in Table 4.

HSBC and SiHSBC samples were exposed to 80° C. water for 12 hours. The properties of the samples with and without water exposure were measured and reported in Table 5.

Peel adhesion tests for SiHSBC on glass substrates were performed by compression molding a 2 mm plate of SiHSBC onto the glass substrate at 180° C. for 5 minutes. Table 6 shows the results.

A comparison of peel adhesion performance of HSBC, SiHSBC and maleic anhydride functionalized HSBC is shown in Table 7. A 2 mm plate of each sample is compression molded onto a glass substrate.

SiHSBC was mixed with toluene at a concentration of 10% by weight to obtain a primer. The resulting primers were applied to glass substrates to study the peel adhesion and transparency of the primers on glass substrates, as shown in Table 8.

A thermoplastic polymer composition was prepared by dry blending SiHSBC with a thermoplastic elastomer compound (TPEC). 2 mm plates of thermoplastic polymer composition were obtained at temperatures between 180°C and 230°C. These plates were compression molded onto a glass substrate at 200° C. for 5 minutes and the peel adhesion strength was measured. Details are shown in Table 9.

As shown in Table 10, the peel adhesion performance of the thermoplastic polymer composition was evaluated on various substrates. The mold was preheated to 70°C and the thermoplastic polymer composition was directly injection overmolded onto each substrate at 240°C. The peel adhesion was measured after storing the substrate with the composition for 1 day at room temperature.

As used herein, the term "comprising" is meant to include the elements or steps identified after the term, but is not exhaustive of any such elements or steps; An embodiment can include other elements or steps. While the terms "comprise" and "including" are used to describe various aspects herein, the terms "consisting essentially of" and "consisting of" of)” can be used in place of “comprises” and “includes” to provide a clearer aspect of the disclosure and is also disclosed.

Claims (15)

a silane-functionalized block copolymer, wherein, based on the total weight of the silane-functionalized block copolymer,
(a) 80-99.90 wt% hydrogenated styrene block copolymer, and (b) 0.1-20 wt% silane,
The silane has the following general formula (I)
RR′ _n SiX _3-n (I)
wherein R is an alkene or alkyne group, R' is H or an alkane group, X is an alkoxy group, and n = 0, 1 or 2;
said hydrogenated styrene block copolymer is obtained by hydrogenating a styrene block copolymer comprising at least one polymer block A derived from a vinyl aromatic monomer and at least one polymer block B derived from a conjugated diene monomer;
The polymer block B is
a hydrogenation level greater than 95 mol% relative to the total moles of the polymerized conjugated diene monomers in the polymer block B, and greater than 80% by weight relative to the total weight of the polymerized conjugated diene monomers in the polymer block B having an amount of polymerized 1,3-butadiene monomer;
The hydrogenated styrene block copolymer is
having a rubbery aliphatic methyl index of 18 to 38 and a polystyrene content of 8 to 45% by weight relative to the total weight of said hydrogenated styrenic block copolymer;
The silane-functionalized block copolymer is
having a peel adhesion strength to a glass substrate greater than 20 N/cm measured according to ASTM F88;
Silane-functionalized block copolymers. 2. The hydrogenated styrenic block copolymer of claim 1, wherein the hydrogenated styrenic block copolymer has an order-disorder transition temperature of less than 300° C. and a melt flow rate of greater than 1 dg/min at 190° C. with a load of 2.16 kg measured according to ASTM D1238. of silane-functionalized block copolymers. Said hydrogenated styrene block copolymer has a viscosity of 1800 mPa.s at 25% by weight in toluene at 25°C. 3. The silane-functionalized block copolymer of claim 1 or 2, having a solution viscosity of less than or equal to s. The hydrogenated styrene block copolymer has a molecular weight M _p of 40-500 kg/mol, the polymer block A has a molecular weight M _{p of 3-45 kg/mol and the polymer block B has a molecular weight M p} of 5-400 kg/mol. 3. The silane-functionalized block copolymer of claim 1 or 2, having M _p . The silane-functionalized block copolymer of claim 1 or 2, wherein the silane-functionalized block copolymer has a refractive index of 1.45-1.55. The vinyl aromatic monomer is styrene, α-methylstyrene, methylstyrene, p-methylstyrene, ethylstyrene, propylstyrene, butylstyrene, tert-butylstyrene, dimethylstyrene, halogenated styrene, methoxystyrene, acetoxystyrene, vinyl selected from the group of toluene, isomers of vinyltoluene, vinylxylene, 1,1-vinylbiphenyl, vinylnaphthalene, vinylanthracene and mixtures thereof, wherein said conjugated diene monomer is 1,3-butadiene, isoprene, 2,3 -dimethyl-1,3-butadiene, 1-phenyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 3-butyl-1,3-octadiene, myrcene, farnesene, 1,3-cyclo 3. The silane-functionalized block copolymer of claim 1 or 2 selected from the group of hexadienes, piperylenes and mixtures thereof. The silane-functionalized block copolymer of claim 1 or 2, wherein the silane-functionalized block copolymer comprises 0.1 to 10% by weight of silane grafted onto the block copolymer relative to the total weight of the silane-functionalized block copolymer. block copolymer. 3. The method of claim 1 or 2, wherein said polymer block A has a hydrogenation level of less than 30 mol % and said polymer block B has a hydrogenation level of more than 70 mol %, relative to the total moles of said hydrogenated styrene block copolymer. A silane-functionalized block copolymer as described. The styrene block copolymer is AB, ABA, (AB) _n X, (ABB') _n X, where A is a polystyrene block, and B and B' are are the same or different and are selected from the group of polybutadiene, poly(isoprene-r-butadiene) and poly(butadiene-r-styrene), where n is a positive integer and X is the residue of the coupling agent) and mixtures thereof. the silane is vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyldimethoxyethoxysilane, vinyldimethoxybutoxysilane, vinyldiethoxybutoxysilane, allyltrimethoxysilane, allyltriethoxysilane, vinyltriacetoxysilane; 1. Selected from the group of methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, dimethoxymethylsilane, diethoxymethylvinylsilane, p-styryltrimethoxysilane, p-styryltriethoxysilane and mixtures thereof. or the silane-functionalized block copolymer according to 2. The silane-functionalized block copolymer according to claim 1 or 2, wherein said silane-functionalized block copolymer has a molecular weight (M _p ) of 45-250 kg/mol. A thermoplastic polymer composition comprising, based on the total weight of the thermoplastic polymer composition:
5 to 95 parts by weight of the silane-functionalized block copolymer of claim 1 or 2 and 5 to 95 parts by weight of a thermoplastic elastomer blend,
The thermoplastic elastomer compound comprises 100 parts by weight of one or more thermoplastic elastomers, and 50 to 250 parts of a plasticizer and 0 to 50 parts of at least one thermoplastic elastomer per 100 parts by weight of the thermoplastic elastomer. containing additives,
said thermoplastic elastomer is selected from the group consisting of polyolefins, hydrogenated styrene block copolymers, styrene block copolymers, thermoplastic copolyesters or copolyester-ethers, thermoplastic vulcanizates, thermoplastic polyurethanes and mixtures thereof;
A thermoplastic polymer composition. 100 parts of the silane-functionalized block copolymer of claim 1 or 2, and for 100 parts by weight of the silane-functionalized block copolymer,
0 to 150 parts of polyolefin,
A thermoplastic polymer composition comprising 30-300 parts of a plasticizer selected from the group consisting of vegetable oils, process oils, mineral oils, phthalates and mixtures thereof, and 0-50 parts of at least one additive. 100 parts of the silane-functionalized block copolymer of claim 1 or 2, and for 100 parts by weight of the silane-functionalized block copolymer,
polypropylene, ethylene-propylene copolymers, high density polyethylene (HDPE), low density polyolefin (LDPE), linear low density polyethylene (LLDPE), ultra high molecular weight polyethylene (UHMW-PE), very low density polyethylene (VLDPE) and their 10-150 parts of a polyolefin selected from the group of mixtures,
A thermoplastic polymer composition comprising 0 to 300 parts of a plasticizer and 0 to 50 parts of at least one additive. An article comprising the silane-functionalized block copolymer of claim 1 or 2.